熔融制样-X射线荧光光谱法测定硅藻土中6种主次组分
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摘要
硅藻土是一种重要的非金属矿产,其主次组分的测定一般采用重量法、滴定法等,操作过程繁琐、化学试剂用量大、分析周期长。实验采用熔融法制样,X射线荧光光谱法(XRF)同时测定硅藻土中SiO_2、Al_2O_3、Fe_2O_3、CaO、MgO、TiO_2等主次组分。选择高纯试剂人工合成校准样品系列,用测定烧失量后的样品制备玻璃熔片,克服了缺少硅藻土标准物质及烧失量对测定结果的影响。样品与四硼酸锂-偏硼酸锂-氟化锂混合熔剂(质量比为4.5∶1∶0.4)的稀释比为1∶10,LiBr溶液作为脱模剂,在1 050℃熔融9min制备熔融片。各组分校准曲线的线性相关系数在0.996 2～0.999 9之间;方法检出限在18～266μg/g之间。按照实验方法测定硅藻土样品中SiO_2、Al_2O_3、Fe_2O_3、CaO、MgO、TiO_2,测定结果的相对标准偏差(RSD,n=8)在0.25%～1.4%之间。所建方法应用于相近标准物质(GBW03103软质粘土和GBW03114硅质砂岩)和4种不同品位的硅藻土样品中各组分的测定,测定结果与标准物质认定值或实际样品湿法测定值基本一致。
Diatomite is an important non-metallic mineral.Its major and minor components are usually determined by gravimetric method and titration method.However,these methods have some disadvantages such as cumbersome operation,large consumption of chemical reagents and long analysis period.The simultaneous determination method of major and minor components(including SiO_2,Al_2O_3,Fe_2O_3,CaO,MgO and TiO_2)in diatomite by X-ray fluorescence spectrometry(XRF)with fusion sample preparation was studied.The standard sample series were artificially synthesized with high purity reagents.The glass beads were prepared using samples after loss on ignition(LOI)test,which overcame the lack of diatomite reference materials and the interference of LOI on analysis results.The dilution ratio of sample to mixed flux(Li_2B_4O_7-LiBO_2-LiF with mass ratio of 4.5∶1∶0.4)was 1∶10.The LiBr solution was added as the releasing agent.The sample was fused at 1 050℃for 9 min to prepare the glass beads.The correlation coefficients of calibration curves of components were between 0.996 2 and 0.999 9.The detection limit of method was between 18μg/g and 266μg/g.The contents of SiO_2,Al_2O_3,Fe_2O_3,CaO,MgO and TiO_2 in diatomite sample were determined according to the experimental method.The relative standard deviations(RSD,n=8)were between 0.25%and 1.4%.The proposed method was applied to the determination of similar certified reference materials and four actual diatomite samples with different grades.The found results were basically consistent with the certified values or those obtained by wet chemical analyses.
Diatomite is an important non-metallic mineral.Its major and minor components are usually determined by gravimetric method and titration method.However,these methods have some disadvantages such as cumbersome operation,large consumption of chemical reagents and long analysis period.The simultaneous determination method of major and minor components(including SiO_2,Al_2O_3,Fe_2O_3,CaO,MgO and TiO_2)in diatomite by X-ray fluorescence spectrometry(XRF)with fusion sample preparation was studied.The standard sample series were artificially synthesized with high purity reagents.The glass beads were prepared using samples after loss on ignition(LOI)test,which overcame the lack of diatomite reference materials and the interference of LOI on analysis results.The dilution ratio of sample to mixed flux(Li_2B_4O_7-LiBO_2-LiF with mass ratio of 4.5∶1∶0.4)was 1∶10.The LiBr solution was added as the releasing agent.The sample was fused at 1 050℃for 9 min to prepare the glass beads.The correlation coefficients of calibration curves of components were between 0.996 2 and 0.999 9.The detection limit of method was between 18μg/g and 266μg/g.The contents of SiO_2,Al_2O_3,Fe_2O_3,CaO,MgO and TiO_2 in diatomite sample were determined according to the experimental method.The relative standard deviations(RSD,n=8)were between 0.25%and 1.4%.The proposed method was applied to the determination of similar certified reference materials and four actual diatomite samples with different grades.The found results were basically consistent with the certified values or those obtained by wet chemical analyses.
引文
[1]郑水林,孙志明,胡志波,等.中国硅藻土资源及加工利用现状与发展趋势[J].地学前缘,2014,21(5):274-280.ZHENG Shui-lin,SUN Zhi-ming,HU Zhi-bo,et al.The processing and utilization of China diatomite resource and its development trend[J].Earth Science Frontiers,2014,21(5):274-280.
[2]Namor AFDD,Gamouz AE,Frangie S,et al.Turning the volume down on heavy metals using tuned diatomite.Areview of diatomite and modified diatomite for the extraction of heavy metals from water[J].Journal of Hazardous Materials,2012,241-242(4):14-31.
[3]贺与平.原子吸收法测定硅藻土中的铁、钙和镁[J].光谱实验室,1993,10(4):72-75.HE Yu-ping.Determination of iron,calcium and magnesium in diatomite by atomic absorption spectrometry[J].Chinese Journal of Spectroscopy Laboratory,1993,10(4):72-75.
[4]刘守廷.ICP-AES法同时测定硅藻土中Al2O3、Fe2O3、CaO和MgO[J].理化检验:化学分册,1991,27(2):119-120.LIU Shou-ting.Simultaneous determination of Al2O3,Fe2O3,CaO and MgO in diatomite by ICP-AES method[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,1991,27(2):119-120.
[5]张立新,孙有娥.ICP-OES法同时测定硅藻土中硅、铝、铁、钙、镁[J].广州化工,2015,43(20):132-133.ZHANG Li-xin,SUN You-e.Simultaneous determination of diatomite in silicon,aluminum,iron,calcium and magnesium by ICP-OES method[J].Guangzhou Chemical Industry,2015,43(20):132-133.
[6]吉昂.X射线荧光光谱三十年[J].岩矿测试,2012,31(3):383-398.JI Ang.Development of X-ray fluorescence spectrometry in the 30years[J].Rock and Mineral Analysis,2012,31(3):383-398.
[7]邢玉富.X射线荧光光谱法测定硅藻土中的主元素[J].化学世界,1994(11):597-599.XING Yu-fu.Determination of major elements in diatomite by X-ray fluorescence spectrometry[J].Chemical World,1994(11):597-599.
[8]单婷婷,孙杨,苏丹,等.熔融制样-X射线荧光光谱法测定硅藻土中主次量元素[J].吉林地质,2016,35(3):109-111.SHAN Ting-ting,SUN Yang,SU Dan,et al.Determination of major and minor elements in diatomite by X-ray fluorescence spectrometry with fusion sample method[J].Jilin Geology,2016,35(3):109-111.
[9]张莉娟,刘义博,李小莉,等.超细粉末压片法-X射线荧光光谱测定水系沉积物和土壤中的主量元素[J].岩矿测试,2014,33(4):517-522.ZHANG Li-juan,LIU Yi-bo,LI Xiao-li,et al.Determination of major elements in stream sediments and soils by X-ray fluorescence spectrometry using pressed-superfine powder pellets[J].Rock and Mineral Analysis,2014,33(4):517-522.
[10]Ichikawa S,Nakamura T.Approaches to solid sample preparation based on analytical depth for reliable X-ray fluorescence analysis[J].X-Ray Spectrometry,2016,45(6):302-307.
[11]曲月华,王一凌,亢德华,等.X射线荧光光谱法测定膨润土中主次成分[J].冶金分析,2009,29(10):13-16.QU Yue-hua,WANG Yi-ling,KANG De-hua,et al.Determination of major and minor components in bentonite by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2009,29(10):13-16.
[12]木士春.中国陆相硅藻土物化特征及对硅藻生长、堆埋环境指示意义[J].湘潭矿业学院学报,2002,17(3):16-21.MU Shi-chun.Physical and chemical characteristics of diatomaceous earth in China and their environmental indications in growth and burying of diatoms[J].Journal of Xiangtan Mining Institute,2002,17(3):16-21.
[13]李国会,李小莉.X射线荧光光谱分析熔融法制样的系统研究[J].冶金分析,2015,35(7):1-9.LI Guo-hui,LI Xiao-li.Systematic study on the fusion sample preparation in X-ray fluorescence spectrometric analysis[J].Metallurgical Analysis,2015,35(7):1-9.
[2]Namor AFDD,Gamouz AE,Frangie S,et al.Turning the volume down on heavy metals using tuned diatomite.Areview of diatomite and modified diatomite for the extraction of heavy metals from water[J].Journal of Hazardous Materials,2012,241-242(4):14-31.
[3]贺与平.原子吸收法测定硅藻土中的铁、钙和镁[J].光谱实验室,1993,10(4):72-75.HE Yu-ping.Determination of iron,calcium and magnesium in diatomite by atomic absorption spectrometry[J].Chinese Journal of Spectroscopy Laboratory,1993,10(4):72-75.
[4]刘守廷.ICP-AES法同时测定硅藻土中Al2O3、Fe2O3、CaO和MgO[J].理化检验:化学分册,1991,27(2):119-120.LIU Shou-ting.Simultaneous determination of Al2O3,Fe2O3,CaO and MgO in diatomite by ICP-AES method[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,1991,27(2):119-120.
[5]张立新,孙有娥.ICP-OES法同时测定硅藻土中硅、铝、铁、钙、镁[J].广州化工,2015,43(20):132-133.ZHANG Li-xin,SUN You-e.Simultaneous determination of diatomite in silicon,aluminum,iron,calcium and magnesium by ICP-OES method[J].Guangzhou Chemical Industry,2015,43(20):132-133.
[6]吉昂.X射线荧光光谱三十年[J].岩矿测试,2012,31(3):383-398.JI Ang.Development of X-ray fluorescence spectrometry in the 30years[J].Rock and Mineral Analysis,2012,31(3):383-398.
[7]邢玉富.X射线荧光光谱法测定硅藻土中的主元素[J].化学世界,1994(11):597-599.XING Yu-fu.Determination of major elements in diatomite by X-ray fluorescence spectrometry[J].Chemical World,1994(11):597-599.
[8]单婷婷,孙杨,苏丹,等.熔融制样-X射线荧光光谱法测定硅藻土中主次量元素[J].吉林地质,2016,35(3):109-111.SHAN Ting-ting,SUN Yang,SU Dan,et al.Determination of major and minor elements in diatomite by X-ray fluorescence spectrometry with fusion sample method[J].Jilin Geology,2016,35(3):109-111.
[9]张莉娟,刘义博,李小莉,等.超细粉末压片法-X射线荧光光谱测定水系沉积物和土壤中的主量元素[J].岩矿测试,2014,33(4):517-522.ZHANG Li-juan,LIU Yi-bo,LI Xiao-li,et al.Determination of major elements in stream sediments and soils by X-ray fluorescence spectrometry using pressed-superfine powder pellets[J].Rock and Mineral Analysis,2014,33(4):517-522.
[10]Ichikawa S,Nakamura T.Approaches to solid sample preparation based on analytical depth for reliable X-ray fluorescence analysis[J].X-Ray Spectrometry,2016,45(6):302-307.
[11]曲月华,王一凌,亢德华,等.X射线荧光光谱法测定膨润土中主次成分[J].冶金分析,2009,29(10):13-16.QU Yue-hua,WANG Yi-ling,KANG De-hua,et al.Determination of major and minor components in bentonite by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2009,29(10):13-16.
[12]木士春.中国陆相硅藻土物化特征及对硅藻生长、堆埋环境指示意义[J].湘潭矿业学院学报,2002,17(3):16-21.MU Shi-chun.Physical and chemical characteristics of diatomaceous earth in China and their environmental indications in growth and burying of diatoms[J].Journal of Xiangtan Mining Institute,2002,17(3):16-21.
[13]李国会,李小莉.X射线荧光光谱分析熔融法制样的系统研究[J].冶金分析,2015,35(7):1-9.LI Guo-hui,LI Xiao-li.Systematic study on the fusion sample preparation in X-ray fluorescence spectrometric analysis[J].Metallurgical Analysis,2015,35(7):1-9.